CDB 2063

SEPARATION PROCESSE II
CRYSTALLISATION
Dr Taslima Khanam
26 May 2015

TOPIC OUTCOMES
By end of topic, students should be able to

understand the concept of crystallization

understand equilibrium solubility of materials

perform material & heat balance for

crystallization process

understand Nucleation Theories

discuss basis of equipment

describe types of crystallizers

TODAYS LESSON OUTCOMES

By end of lesson, students should be able to

understand the concept of crystallization

understand equilibrium solubility of

materials

perform material balance for

crystallization process

understand Nucleation Theories

3

CRYSTALLISATION THEORY

Crystallization is a particle formation

process by which solute molecules in a
solution are transformed into a solid
phase of regular lattice structure
occurs by precipitation process where
particles form by decreasing solute
solubility (i.e. increasing
supersaturation) by cooling,
evaporation, anti-solvent addition, etc.
mass transfer of a solute from liquid
solution to form pure solid crystalline
phase
4
Key point: solid-liquid separation

APPLICATION
One of the oldest and most important unit operation with
enormous economic importance.
- Widely used in fine chemical and pharmaceutical
industries for purification, separation, production step(s).

OBJECTIVE OF CRYSTALLIZATION
Important objectives in
crystallization

good yield

high purity

size uniformity

minimize caking

ease of pouring

ease of washing
& filtering

uniform behavior

CRYSTAL GEOMETRY

Crystal solid composed of atoms, ions or

molecules which are arranged in
organized, orderly and repetitive manner

appear as polyhedrons

flat faces and sharp corners

All crystals of same material possess

equal angle between the

corresponding faces (particular shape)

relative sizes of faces can be different

Different size and similar shape

same particular characteristics

Geometry important to recognize crystal7

CRYSTAL GEOMETRY
Crystal structure maintain lattice structure
A point lattice is a set of points arranged so that
each point has identical surroundings.
A unit cell is a single cell constructed employing
the same parameters (e.g. bond angles) as those
of lattice.

Point lattice

Unit cell
8

CRYSTAL GEOMETRY

Crystal classification based on the interfacial angle &

length of axes

Seven Crystallographic systems

TYPES OF CRYSTALLINE SOLID

Crystalline solids can be classification based on
type of bond to hold the particles in place in
crystal lattice
i.Ionic crystals - charged ions held in place in the
lattice by electrostatic forces (e.g. sodium
chloride).
ii.Covalent crystals - constituent atoms do not
carry effective charges; connected by a
framework of covalent bonds, the atoms sharing
their outer electrons (e.g. diamond).
iii.Molecular crystals - discrete molecules held
together by weak attractive forces (e.g. VDW
force or H bonds) (e.g. organic compounds,
sugar).
iv.Metallic crystals - ordered arrays of identical10
cations held by sharing of outer electrons

QUESTION?
11

SOLUBILITY IN CRYSTALLIZATION
Solubility - maximum
amount of solute that
can be dissolved in a
given solvent at a
given temperature

EQUILIBRIUM in crystallization is
attained when the solution is
SATURATED
Represented by a SOLUBILITY
Solubility
is
dependent
mainly
on
CURVE
TEMPERATURE
12

SOLUBILITY IN CRYSTALLIZATION
Solubility measurements
Polythermal methods heating
solutions initially containing excess
solutes.
Isothermal methods adding
solvents at constant temperature.
Magnitude of solubility depends on unit
used.
Mass (or moles) solute/mass (or
moles) solvent
Mass (or moles) solute/mass (or
13
moles) solution

SOLUBILITY CHART

line = saturated
above line = supersat
below line = undersat
generally, the
solubilities of
most salts
increase with
increasing
temperature
but can be
otherwise

14

SUPERSATURATION

Saturated solution

Solution that is in
thermodynamic
equilibrium with
the solid phase of
its solute at a
given
temperature.
Supersaturated
solution
Solution containing more dissolved solute than that
given by the equilibrium saturation value.

Degree of supersaturation (conc. driving force) is

given by: c = c cs (molar concentration); or y =
y ys (molar fraction)
where c and cs are the solution conc., and equilibrium
15
saturation conc. at a given T, respectively.

GENERATION OF SUPERSATURATION
Techniques to generate supersaturation
COOLING

SOLVENT
EVAPORATIO
N
SALTING

PRECIPITATI
ON

If solute solubility increase strongly

with increase temperature,
supersaturation generated by
temperature reduction

If solubility is independent of
temperature, supersaturation
generated by evaporating a
portion
of the
solvent
If
solubility
is very
high (NEITHER
cooling & evaporation is desirable),
supersaturation is generated by
addition of common ion salt to
decrease solubility. (e.g. adding ammonium
If
a nearly
complete
sulphate
to protein
solution) precipitaion is
required, supersaturation
generated by chemical reaction16 by
adding third component. (e.g. hydrolysis

FORMATION OF CRYSTALS
Prerequisites

for the formation of crystal is

supersaturation

formation

of crystals - 2 steps :

1.

birth of new particle - nucleation

2.

its growth to macroscopic size

neither

crystal growth nor formation of nuclei

from the solution can occur in a saturated or
unsaturated solution

driving

potential for both rates is

supersaturation
17

FORMATION OF CRYSTALS

Formation of solid crystals from

homogeneous solution
Concentration of solute, C

Solubility curve
[saturation
concentration, C*(T)]

Temperature, T

18

FORMATION OF CRYSTALS

Formation of solid crystals from

homogeneous solution
Concentration of solute, C

Solubility curve
[saturation
concentration, C*(T)]
A

Undersaturated
Temperature, T

19

FORMATION OF CRYSTALS

Formation of solid crystals from

homogeneous solution
Concentration of solute, C

Solubility curve
[saturation
concentration, C*(T)]
A

Supersaturated
Temperature, T

20

FORMATION OF CRYSTALS

Formation of solid crystals from

homogeneous solution
Concentration of solute, C

Metastable
zone
Solubility curve
[saturation
concentration, C*(T)]

Metastable
limit
C

Nucleation

Temperature, T

Metastable limit is influenced by saturation temperature,

rate of supersaturation generation, impurity level, mixing
For nucleation in metastable zone, seeding (adding small
crystal particles) is required.

21

FORMATION OF CRYSTALS

Formation of solid crystals from

homogeneous solution
Concentration of solute, C

Metastable
zone

Growth

Solubility curve
[saturation
concentration, C*(T)]

Metastable
limit
C

D
Temperature, T

22

QUESTION?
23

YIELD & MATERIAL BALANCE

material

balance is
straightforward if
solutes

in

are anhydrous

crystallization

some

water is removed as

water
some

water in the solution

is removed with the
crystals as hydrate
24

MATERIAL BALANCE
W kg H2O
L kg solution
(solute + solvent)

COOLER &
CRYSTALLIZER

S kg solution
xi,S
C kg crystals
xi,C
25

MATERIAL BALANCE

L kg solution
xi,L

W kg H2O
= 0 (no evap)
xi,W
COOLER &
CRYSTALLIZER

L xi , L S xi , S W xi ,W C xi ,C
i water, solute

S kg solution
xi,S
C kg crystals
xi,C
26

MATERIAL BALANCE
Example:
A salt solution weighing 10 000 kg
with 30% Na2CO3 is cooled to 293 K
(20C). The salt crystallizes as the
decahydrate. What will be the yield
of Na2CO310H2O crystals if the
solubility is 21.5 kg anhydrous
Na2CO3 per 100 kg of total water?
Assume that no water is evaporated. 27

MATERIAL BALANCE
W kg H2O
=0, no evap.
10,000 kg
solution
30% Na2CO3

COOLER &
CRYSTALLIZER

S kg soln
21.5 kg Na2CO3/
100 kg H2O

Molecular Weight:
10H2O = 180.2
Na2CO3 = 106
Na2CO3 10H2O = 286.2

C kg crystals,
Na2CO310H2O
28

MATERIAL BALANCE
1. Perform material balance for water and Na2CO3
Feed = Solution stream + Crystals stream + Vapor stream
Feed stream: given
Solution stream
Given: 21.5 kg Na2CO3 per 100 kg H2O in Solution stream
xwater , S

kg Na 2CO3
kg H2O
, x Na2CO3 , S

kg H2O kg Na 2CO3
kg H2O kg Na 2CO3

Crystal stream contains Na2CO310H2O

xwater ,C

MW Na 2CO3
MW H2O
, xNa 2CO3 ,C

MW Na 2CO3 10H2O
MW Na 2CO3 10H 2O

Vapor stream
W = 0 as no evaporation

29

MATERIAL BALANCE
Feed = Solution stream + Crystals stream + Vapor stream

L xi , L S xi , S W xi ,W C xi ,C
i water, solute
Water:

Na2CO3:

100
180.2
0.7(10000)
(S )
(C ) 0
100 21.5
286.2
21.5
106
0.3(10000)
(S )
(C ) 0
100 21.5
286.2
30

MATERIAL BALANCE
2. Solving the two equation simultaneously,
C = 6370 kg of Na2CO310H2O crystals
S = 3630 kg solution

31

MATERIAL BALANCE

Assume that 6% of the total weight of

the solution is LOST by evaporation
of water in cooling, recalculate C and
S ????

32

HEAT BALANCES IN CRYSTALLIZATION

Feed,
H1

q = (H2 + HV) H1

Hv , Water
vapor
CRYSTALLIZER

Two phase mixture

(crystal + saturated
solution), H2

H1

=
enthalpy of the entering solution (feed) at
the initial temperature

H2

=
enthalpy of the final mixture of crystals and
mother liquor at the final temperature

HV

=
enthalpy of water vapor (if evaporation
occurs)

total heat transferred (kJ) (+ve: heat must 33

Example
A feed of 10000 lbm solution is flowed
into the system at 130F. The
concentrated solution is flowed out at
80F. The yield of crystals FeSO4.7H2O
is 2750 lbm. The average heat capacity
of the feed is 0.70 btu/lbmF. The heat
of solution at 80F is -28.47 btu/lbm
Heat of feed, H1 = 10000(0.70)(130-80) = 350000 btu
FeSO4.7H2O.

Heat of crystallization, H2
= 28.47 2750 lbm FeSO4.7H2O
= 78300 btu
34

Example

Heat transferred, q = (H2 + HV) H1

= 78300 + 0 350000
= 428300 btu
Since q is ve, heat is removed
(exothermic)

35